KR102187174B1 - Plasticizer composition and resin composition comprising the same - Google Patents

Abstract

The present invention relates to a citrate-based plasticizer and a resin composition comprising the same, wherein the citrate-based plasticizer includes one or more citrates having an alkyl group having 7 carbon atoms. The citrate plasticizer may solve problems of transferability and heating loss contained in existing plasticizers, problems in processing characteristics such as plasticization efficiency and absorption rate, and may have excellent quality reproducibility.

Description

Citrate plasticizer and resin composition comprising the same {PLASTICIZER COMPOSITION AND RESIN COMPOSITION COMPRISING THE SAME}

The present invention relates to a citrate plasticizer and a resin composition comprising the same.

Typically plasticizers react with alcohols with polycarboxylic acids such as phthalic acid and adipic acid to form corresponding esters. Commercially important examples are adipates of C8, C9 and C10 alcohols such as di(2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate; And phthalates of C8, C9 and C10 alcohols such as di(2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate.

Specifically, the di(2-ethylhexyl) phthalate is a toy, film, shoe, paint, flooring, gloves, wallpaper, artificial leather, sealant, tarpaulin, car floor coating, furniture, through a dry blending of plastisol and dry formula. It is used in the manufacture of foam mats, and sound insulation panels, and can also be used to produce sheathing and insulation of PVC cables, and other calendered plastic PVC products.

Ester compounds currently used as plasticizers include di-(2-ethylhexyl) phthalate (DEHP), di-isononyl phthalate (DINP), di-2-propylheptyl phthalate (DPHP), or diisodecyl phthalate (DIDP). Although widely used, these products are harmful to the human body as environmental hormones that disturb the endocrine system, and depending on the use, there are limitations in improving product properties in terms of processability with resin, absorption rate, volatilization loss, migration loss, and thermal stability. .

On the other hand, citrate is mainly applied as a secondary plasticizer to improve the physical properties of general-purpose plasticizers, and citrate is typically used as a raw material of C2 to C4 alcohol. However, due to problems such as transferability and heating loss of these products, it is difficult to apply as a single plasticizer or a plasticizer applied in a high content as a primary plasticizer. In addition, if the carbon number of the raw material alcohol is increased to improve such physical properties, it can be expected that it will adversely affect the plasticization efficiency and the like.

In addition, in order to improve these problems, citrate having an alkyl group having different carbon atoms may be used as a single plasticizer, but in this case, there is a problem that it is difficult to commercialize a product due to economic reasons resulting from an increase in manufacturing cost and a complicated manufacturing process.

Therefore, it is an eco-friendly or non-phthalate-based compound that can sufficiently improve the physical properties of existing products in terms of various physical properties such as volatilization loss, migration loss and thermal stability as well as processability, absorption rate, hardness, tensile strength, and elongation of the resin. It is in need of development.

In the present invention, as a plasticizer applied to a resin composition, it is intended to provide a citrate-based plasticizer containing citrate as a main component as an eco-friendly plasticizer as an eco-friendly material as a plasticizer with excellent reproducibility of physical properties while improving physical properties such as plasticization efficiency, migration resistance and heating loss. do.

In order to solve the above problems, according to an embodiment of the present invention, a citrate plasticizer comprising at least one compound represented by the following formula (1) is provided.

[Formula 1]

In Formula 1, R ₁ to R ₃ are each independently an alkyl group having 7 carbon atoms.

According to an embodiment of the present invention in order to solve the above problem, 100 parts by weight of a resin; And 5 to 150 parts by weight of the citrate-based plasticizer described above.

When the citrate plasticizer according to an embodiment of the present invention is used in a resin composition, it is eco-friendly and has excellent plasticization efficiency and excellent processability due to an appropriate absorption rate, and provides excellent physical properties in migration resistance, heating loss, and volatility resistance. The citrate plasticizer may have excellent quality reproducibility.

Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.

The terms or words used in the description and claims of the present invention should not be construed as being limited to their usual or dictionary meanings, and the inventors appropriately explain the concept of terms in order to explain their own invention in the best way. Based on the principle that it can be defined, it should be interpreted as a meaning and concept consistent with the technical idea of the present invention.

Citrate Plasticizer

According to an embodiment of the present invention, a citrate plasticizer containing at least one compound represented by the following formula (1) is provided.

[Formula 1]

In Formula 1, R ₁ to R ₃ are each independently an alkyl group having 7 carbon atoms.

R ₁ to R ₃ of Formula 1 may each independently be any one of an n-heptyl group and a 2-methylhexyl group. In the present specification, the '2-methylhexyl group' may be conventionally referred to as an'isoheptyl group' in the art, but it is a substituent having a structure in which a methyl group is bonded to carbon 2 of the hexyl group according to the chemical structural formula. 'TiHC' may be used as an English abbreviation for late, which may mean triisoheptyl citrate, and a 2-methylhexyl group in three alkyl substituents (R ₁ to R ₃ in Formula 1 above) of citrate May mean a compound having a bonded structure.

On the other hand, when citrate is applied as a primary plasticizer, that is, when applied as a single plasticizer or in a high content, citrate with a small carbon number has a very low molecular weight and high volatility, so heating loss or transferability is quite poor. And, when the number of carbon atoms is too large, plasticization efficiency and absorption rate are not good, so there is a problem in processability, and it is generally applied as a secondary plasticizer to compensate.

In addition, citrates with alkyl groups having different carbon atoms bound essentially undergo a transesterification reaction, and in this case, a total of 6 types of products are produced, and their separation is practically impossible, so a mixture of these is applied when commercializing them. It is common to do.

However, the ratio between the mixtures may vary depending on the alcohol content or reaction conditions, and due to such a change in the ratio, the overall average molecular weight or the degree of branching of the alkyl group is changed, so that the final physical properties are not uniform. There is a problem of falling. In the case of applying citrate with different carbon number of the alkyl group due to various factors for changing physical properties, it is a situation that it is somewhat difficult to control the quality of the product and to ensure uniform quality. To solve this problem, control of process conditions, etc. In the case of supplementation, economic problems such as separate process costs occur.

However, the citrate plasticizer according to the present invention is to which an alkyl group having 7 carbon atoms is applied, and the plasticization efficiency or absorption rate is so excellent that citrate can be used as a single plasticizer, so that the processability can be improved, and transfer characteristics and heating The weight loss can also show a level equal to or higher than that of the existing plasticizer. In addition, since the number of carbon atoms of the alkyl group is not different and the same, it is possible to provide a plasticizer having excellent product quality reproducibility.

In the present specification, "immobilized citrate" may mean a citrate in which R ₁ to R ₃ are all the same alkyl group in Chemical Formula 1, and "hybrid citrate" is that R ₁ to R ₃ are different from each other, R ₁ And R ₂ is the same but different from R ₃ , R ₂ and R ₃ may be the same but different from R ₁ .

The citrate plasticizer may include one or more selected from the group consisting of compounds represented by the following Formulas 1-1 to 1-6.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

Specifically, the citrate-based plasticizer may be a plasticizer containing one type of citrate or two types of citrate. In this case, the citrate may be a plasticizer including an immiscible citrate represented by Formula 1-1 or an immiscible citrate represented by Formula 1-2 below, or a plasticizer including both materials.

In addition, the citrate-based plasticizer may include three or more types of citrate, and in this case may be a citrate-based plasticizer including all of the Chemical Formulas 1-1 to 1-6.

As described above, when the citrate-based plasticizer is used in a high content as the sole plasticizer or primary plasticizer of the resin composition, plasticization efficiency (hardness) and tensile strength are equivalent to those of phthalate-based compounds that are mainly used as plasticizers. Not only can the environmental problem be solved by securing the elongation and elongation, but also the excellent absorption rate can serve as a basis for improving workability along with excellent plasticization efficiency. In addition, heating loss may be reduced and migration resistance may be remarkably excellent.

In addition, it is preferable that the citrate-based compounds are not acetyl citrate to which an acetyl group is bonded instead of hydrogen of a hydroxy group (-OH). That is, the acetyl group may not exist in the molecule, and it is preferable to use a citrate compound in which the acetyl group is not bonded. When an acetyl group is present in the citrate-based compound, there is a concern that the physical properties of the plasticizer, especially the processability and gelling properties due to the decrease in plasticizing efficiency, may deteriorate, and the addition of an increased amount of plasticizer to overcome the decrease in the plasticization efficiency. Due to problems such as an increase in product price, there may be adverse effects in various aspects such as marketability, economic feasibility, and physical properties.

Meanwhile, although not limited thereto, when the citrate-based plasticizer contains three or more citrates, 3.0 to 99.0 mol% of non-mixed citrate represented by Formula 1-1; 0.5 to 96.5 mol% of the first hybrid citrate and the second hybrid citrate represented by Chemical Formulas 1-3 to 1-6; And 0.5 to 96.5 mol% of non-mixed citrate represented by Formula 1-2.

When the citrate plasticizer is applied as a mixture as described above, it is contained within the molar ratio range as described above, so that it is environmentally friendly and has an appropriate absorption rate for the resin and a short melting time to further improve the processability of the resin, and hardness and migration loss. , Heat loss, and other physical properties can be improved.

Citrate Manufacturing method of plasticizer

According to an embodiment of the present invention, a citrate plasticizer may be obtained by direct esterification reaction between citric acid and alcohol, or transesterification reaction between a compound represented by the following formula (1) and an alcohol.

[Formula 1]

In Formula 1, R ₁ to R ₃ are each independently an alkyl group having 7 carbon atoms.

More specifically, in the case of preparing a citrate-based plasticizer containing the compound of Formula 1-1 or Formula 1-2, a direct esterification reaction may be applied. Citric acid and n-heptyl alcohol or 2-methylhexyl alcohol Can be prepared by directly carrying out the esterification reaction using. That is, as a method of preparing an immiscible citrate, a direct esterification reaction may be performed, and in the case of a citrate-based plasticizer containing the compounds of Formulas 1-1 and 1-2, a method of preparing and blending each Can be employed.

The direct esterification reaction is carried out in a temperature range of 80 to 270, preferably in a temperature range of 150 to 250, at 10 minutes to 10 hours, preferably 30 minutes to 8 hours, more preferably 1 to 6 hours. desirable.

The catalyst for the direct esterification reaction may be an organometallic catalyst including Sn or Ti, an acid catalyst including a sulfonic acid or sulfuric acid, or a mixed catalyst thereof, and is not limited to the type of catalyst.

The citric acid and the alcohol are preferably used in an amount of 1:1 to 7 molar ratio, preferably in an amount of 1:2 to 5 molar ratio.

By the direct esterification reaction for the preparation of the citrate, citrate may be prepared in a yield of about 80% or more.

In particular, in the case of using butanol to apply a citrate plasticizer having a small carbon number, for example, to apply a citrate plasticizer containing a butyl group, butanol having a low boiling point must be present from the beginning of the reaction as the first raw material. , Due to the low boiling point of butanol, before reaching the catalyst activation temperature, which is the temperature at which the esterification reaction proceeds normally, butanol vaporizes and does not participate in the reaction, and only circulation in the process may occur. However, in the case of the citrate plasticizer according to the present invention, the use of butanol is not required, and the generation of wastewater containing alcohols having high solubility in water such as butanol can be avoided, and accordingly, energy costs or process costs are secondary. Etc. can be saved.

In addition, when the citrate-based plasticizer includes all of the compounds of Formulas 1-1 to 1-6, a direct esterification reaction using a mixture of alcohols having 7 carbon atoms may be performed.

The direct esterification reaction using a mixed alcohol may be more efficient than the transesterification reaction.In the case of an alcohol having 7 carbon atoms, in the prepared state, unless a separate purification process is performed, a mixture of alcohols having 7 carbon atoms (the main component is It may be n-heptanol and 2-methylhexanol, and as a secondary alcohol, isomers having 7 carbon atoms may be included together), and accordingly, according to the present invention, a mixed alcohol not subjected to a purification process may be used. Since the desired effect can be achieved even by preparing a citrate plasticizer, a direct esterification reaction through a mixed alcohol without performing a separate purification process can be preferably applied.

On the other hand, in addition to the direct esterification reaction, a citrate plasticizer may be prepared through a transesterification reaction, and an alkyl group different from the immiscible citrate of Formula 1-1 or Formula 1-2 and the alkyl group of the citrate A transesterification reaction in which an alcohol having is reacted may be performed.

For example, when the compound of Formula 1-1 is selected as an immiscible citrate, it can be reacted with 2-methylhexyl alcohol, and when the compound of Formula 1-2 is selected as an immiscible citrate, n-heptyl alcohol It may be to react with.

As used in the present invention, "transesterification reaction" refers to a reaction in which an alcohol and an ester react as shown in Scheme 1 below, and R" of an ester is interchanged with R'of an alcohol as shown in Scheme 1 below:

[Scheme 1]

For example, when the alcohol is 2-methylhexyl alcohol and the citrate is tri(n-heptyl) citrate of Formula 1-1, when the trans-esterification reaction is performed, the 2-methylhexanoxide of the alcohol is By attacking all the carbonyl carbons of the three n-heptyl (RCOOR") groups present in the rate, a citrate-based compound represented by Formula 1-2 can be formed; the carbonyl of two n-heptyl groups When attacking carbon, a compound represented by Chemical Formulas 1-5 or 1-6 may be formed; When attacking a carbonyl carbon of one n-heptyl (RCOOR") group, Chemical Formula 1-3 or Can form a compound represented by 1-4; As an unreacted moiety in which no reaction has been made, it may remain as a compound represented by Formula 1-1.

In the case of producing a citrate-based plasticizer using the transesterification reaction as described above, the reaction time may be greatly shortened.

According to an embodiment of the present invention, the citrate plasticizer prepared by the transesterification reaction may include all of the citrate compounds represented by Formulas 1-1 to 1-6, and the amount of alcohol added Accordingly, the composition ratio of the compounds in the citrate-based composition can be controlled.

The amount of the alcohol added may be 0.1 to 89.9 parts by weight, specifically 3 to 50 parts by weight, and more specifically 5 to 40 parts by weight based on 100 parts by weight of the citrate.

When the citrate plasticizer is a mixture and contains all of the citrates of Formula 1-1 to Formula 1-6, the greater the amount of alcohol added, the greater the mole fraction of citrate, a reactant participating in the transesterification reaction. As it will become larger, the content of the hybrid citrate as a product can be increased.

In addition, accordingly, the content of citrate present as unreacted may tend to decrease.

According to an embodiment of the present invention, the trans-esterification reaction is 120 to 190, preferably 135 to 180, more preferably 10 minutes to 10 hours under a reaction temperature of 141 to 179, preferably 30 minutes to It is preferable to carry out at 8 hours, more preferably 1 to 6 hours. Within the above temperature and time range, it is possible to effectively obtain a citrate-based composition having a desired composition ratio. In this case, the reaction time may be calculated from the point when the reaction temperature reaches the reaction temperature after raising the temperature.

According to an embodiment of the present invention, the trans-esterification reaction may be carried out without a catalyst, but may be carried out under an acid catalyst or a metal catalyst, and in this case, there is an effect of shortening the reaction time.

The acid catalyst may be, for example, sulfuric acid, methanesulfonic acid, or p-toluenesulfonic acid, and the metal catalyst may be, for example, an organometallic catalyst, a metal oxide catalyst, a metal salt catalyst, or a metal itself.

The metal component may be, for example, any one selected from the group consisting of tin, titanium, and zirconium, or a mixture of two or more of them.

Resin composition

The present invention provides a resin composition comprising the citrate plasticizer and a resin.

According to an embodiment of the present invention, the resin may be a resin known in the art. For example, a mixture of at least one selected from ethylene vinyl acetate, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, thermoplastic elastomer, and polylactic acid may be used, but is not limited thereto.

The citrate plasticizer may be included in an amount of 5 to 150 parts by weight based on 100 parts by weight of the resin.

The resin composition may further include a filler. The filler may be 0 to 300 parts by weight, preferably 50 to 200 parts by weight, more preferably 100 to 200 parts by weight, based on 100 parts by weight of the resin.

The filler may be a filler known in the art, and is not particularly limited. For example, it may be a mixture of one or more selected from silica, magnesium carbonate, calcium carbonate, hard coal, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate, magnesium silicate and barium sulfate.

The resin composition may further include other additives such as a stabilizer if necessary.

Other additives such as the stabilizer may be, for example, 0 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the resin, respectively. The stabilizer may be a calcium-zinc-based (Ca-Zn-based) stabilizer, such as a calcium-zinc complex stearic acid salt, but is not particularly limited thereto.

The citrate plasticizer according to an embodiment of the present invention has an absorption rate for the resin and a short melting time to improve the processability of the resin, and sheets such as wires, automobile interior materials, films, sheets, tubes, wallpaper, toys, flooring materials, etc. It can provide excellent physical properties when prescribing and compounding.

Example

Hereinafter, examples will be described in detail to illustrate the present invention in detail. However, the embodiments according to the present invention may be modified in various forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more completely describe the present invention to those of ordinary skill in the art.

Manufacturing example 1: THC(tree(n- Heptyl ) Citrate ) Of manufacture

Purified 2-hydroxypropane-1,2,3-tricarboxylic acid (2-hydroxypropane-1,2) in a 4-neck 3-liter reactor equipped with a cooler, water stripper, condenser, decanter, reflux pump, temperature controller, stirrer, etc. ,3-tricarboxylic acid) (citric acid) 576 g, n-heptyl alcohol (Aldrich) 1566 g (molar ratio 1:4.5), titanium catalyst (TnBT, tetra nbutyl titanate) as a catalyst 1.44 g (0.25 weight per 100 parts by weight of citric acid) Part) was added, and the temperature was gradually raised to about 170. Generated water began to be generated around 170, and the esterification reaction was performed for about 4.5 hours while nitrogen gas was continuously added under the conditions of a reaction temperature of about 220 and atmospheric pressure, and the reaction was terminated when the acid value reached 0.1.

After completion of the reaction, distillation extraction was performed under reduced pressure for 0.5 to 4 hours in order to remove unreacted raw materials, the reaction solution was cooled, and catalyst neutralization was performed. Thereafter, the reaction solution was dehydrated to remove moisture. Thereafter, the reaction solution was dehydrated to remove moisture. A filter medium was added to the reaction solution from which moisture was removed, stirred for a certain period of time, and filtered to finally obtain 1431 g (yield: 98%) of tri(n-heptyl)citrate (THC).

Manufacturing example 2: Of TiHC (tri(2-methylhexyl) citrate) Produce

In Preparation Example 1, the reaction was carried out in the same manner as in Preparation Example 1, except that 2-methylhexyl alcohol was used instead of using n-heptyl alcohol, and finally tri(2-methylhexyl)citrate (TiHC) 1435 g (yield: 98%) was obtained.

Manufacturing example 3: n- Heptyl And 2- Methylhexyl Citrate Preparation of mixture (THC-1)

The same was carried out except that n-heptyl alcohol and 2-methylhexyl alcohol were used at 5:5 instead of the n-heptyl alcohol of Preparation Example 1 as reaction raw materials. In this case, the citrate mixture contains 26.5 mol% of citrate represented by Formula 1-1, 48.5 mol% of citrate represented by 1-3 and 1-4, and Formulas 1-2, 1.5 and 1 It is a mixture in which citrate expressed as -6 is 25.0 mol%.

Manufacturing example 4: n- Heptyl And 2- Methylhexyl Citrate Preparation of mixture (THC-2)

Transesterification was performed using 1000 g of semi-finished THC and 240 g of 2-methylhexyl alcohol after extraction from which the unreacted material was removed in Preparation Example 1 as a reaction material, and finally 998 g of a mixture of citrate was obtained.

At this time, the citrate mixture contains 54.7 mol% of citrate represented by Formula 1-1, 40.5 mol% of citrate represented by 1-3 and 1-4, and Formulas 1-2, 1.5 and 1 It is a mixture of 4.8 mol% of citrate represented by -6.

Comparative Production Example 1: Preparation of TBC

Using 384 g of citric acid and 580 g of butanol as reaction raw materials, 706 g (yield: 98%) of tributyl citrate was finally obtained.

Comparative Production Example 2: TPC Produce

Using 384 g of citric acid and 688 g of 1-pentanol as reaction raw materials, 796 g (yield: 98%) of tripentyl citrate was finally obtained.

Comparative Production Example 3: THxC Produce

Using 384 g of citric acid and 797 g of n-hexanol as reaction raw materials, 878 g (yield: 98%) of trihexyl citrate was finally obtained.

Comparative Production Example 4: TOC's Produce

384 g of citric acid and 1014 g of 2-ethylhexanol were used as reaction raw materials, and finally 1029 g of tri(2-ethylhexyl citrate) (yield: 98%) was obtained.

Comparative Production Example 5: TiNC Produce

384 g of citric acid and 1123 g of isononanol were used as reaction raw materials, and finally 1111 g of triisobutyl citrate (yield: 98%) was obtained.

Comparative Production Example 6: Of BOC253 Produce

Transesterification was performed using 1000 g of TOC prepared in Preparation Example 6 and 300 g of n-butanol as reaction raw materials, and finally 840 g of butyloctyl citrate was obtained.

The mixture contains about 2.2% by weight of TBC in order of molecular weight, and about 18.7% by weight of two citrates in which two 2-ethylhexyl groups are exchanged with a butyl group, and the sum of these three substances is about 20.9% by weight. And, the sum of the two citrates in which one 2-ethylhexyl group was exchanged with a butyl group was about 45.4% by weight, which was about 5% by weight, and the TOC was about 33.7% by weight, to prepare a mixture in about 3% by weight.

Comparative Production Example 7: Of BOC145 Produce

Transesterification was performed using 1000 g of TOC and 150 g of n-butanol prepared in Preparation Example 6 as reaction raw materials, and finally 940 g of butyloctyl citrate was obtained.

In the order of molecular weight, the mixture contains about 0.7% by weight of TBC and about 9.2% by weight of two citrates in which two 2-ethylhexyl groups are exchanged with a butyl group, and the sum of these three substances is about 9.9% by weight, which is about 1% by weight. And, the sum of the two citrates in which one 2-ethylhexyl group was exchanged with a butyl group was about 38.9% by weight, which was about 4% by weight, and the TOC was about 51.2% by weight, to prepare a mixture in about 5% by weight.

Example 1 to 4 and Comparative example 1 to 7

The citrate prepared in Preparation Examples 1 to 4 was applied as the plasticizer of Examples 1 to 4, and the citrate prepared in Comparative Preparation Examples 1 to 7 was applied as the plasticizer of Comparative Examples 1 to 7, and the applied citrate The number of carbon atoms is summarized in Table 1 below.

Citrate alkyl group carbon number Example 1 7 Example 2 7 Example 3 7 Example 4 7 Comparative Example 1 4 Comparative Example 2 5 Comparative Example 3 6 Comparative Example 4 8 Comparative Example 5 9 Comparative Example 6 4 and 8 Comparative Example 7 4 and 8

<Test items>

Hardness measurement

Using ASTM D2240, the shore (shore “A”) hardness at 25° C., 3T 10s was measured.

Measurement of tensile strength

According to the ASTM D638 method, the cross head speed was pulled at 200 mm/min (1T) using a test instrument UTM (manufacturer; Instron, model name; 4466), and then the point at which the specimen was cut was measured. . Tensile strength was calculated as follows:

Tensile strength (kgf/㎟) = load value (kgf) / thickness (mm) x width (mm)

Elongation (elongation rate) measurement

According to the ASTM D638 method, the cross head speed was pulled at 200 mm/min (1T) using the U.T.M. After measuring the point at which the specimen was cut, the elongation was calculated as follows:

It was calculated as elongation (%) = [length after elongation / initial length] x 100.

Measurement of migration loss

According to KSM-3156, a specimen with a thickness of 2 mm or more was obtained, and a PS plate was attached to both sides of the specimen and a load of 2 kgf/cm2 was applied. The specimen was left in a hot air circulation oven (80°C) for 72 hours and then taken out and cooled at room temperature for 4 hours. Then, after removing the PS attached to both sides of the test piece, the weight before and after leaving it in the oven was measured, and the transfer loss was calculated by the following equation.

Transition loss (%) = [(initial weight of specimen at room temperature-weight of specimen after leaving the oven) / initial weight of specimen at room temperature] x 100

Measurement of volatile loss

The prepared specimen was worked at 100° C. for 72 hours, and then the weight of the specimen was measured.

Heating loss (%) = [(initial specimen weight-specimen weight after work) / initial specimen weight] x 100.

Liquid heating loss measurement

40g of the liquid product was placed in a container with a diameter of 15 centimeters, stored in a convection oven at 125 for 3 hours, and the weight before and after the experiment was measured and calculated.

Stress test

After bending the prepared resin specimen 180 degrees, store it in a chamber fixed at 23, 50% humidity for 72 hours, then take out the specimen and wipe the folded part with oil paper to determine the degree of plasticizer transfer on a scale of 0 to 3. Evaluate.

Experimental example 1: Evaluation of physical properties of the resin specimen

Specimens were prepared using the plasticizers of Examples 1 to 4 and Comparative Examples 1 to 7.

For the preparation of the specimen, referring to ASTM D638, for 100 parts by weight of polyvinyl chloride resin (PVC (LS100S)), 60 parts by weight of the citrate plasticizer prepared in the Examples and Comparative Examples, and BZ153T as a stabilizer (Songwon Industry ) 3 parts by weight were mixed and mixed at 700 rpm at 98. A specimen was prepared by working at 160 for 4 minutes using a roll mill, and working at 180 for 2.5 minutes (low pressure) and 2 minutes (high pressure) using a press.

Each of the test items was evaluated for the specimen, and the results are shown in Table 2 below.

Hardness
(Shore A) Seal
burglar
(kg/cm ² ) Elongation
(%) implementation
Loss
(%) Liquid
Heating loss
(%) heating
outage
(%) stress
Test
(72hr) Example 1 67.5 168.5 305.8 0.39 0.03 0.86 0 Example 2 67.2 163.6 307.4 0.40 0.04 0.93 0 Example 3 67.3 167.9 307.0 0.38 0.03 0.88 0 Example 4 67.4 166.5 306.2 0.40 0.03 0.90 0 Comparative Example 1 64.5 143.6 275.6 2.67 1.33 3.45 0.5 Comparative Example 2 65.8 148.7 283.3 2.11 1.10 2.87 0.5 Comparative Example 3 66.4 156.9 288.6 1.58 0.87 1.50 0.5 Comparative Example 4 69.6 169.7 298.7 2.35 0.05 0.78 2.0 Comparative Example 5 72.8 165.7 306.2 2.88 0.02 0.60 3.0 Comparative Example 6 67.9 154.3 285.4 1.36 0.76 1.37 1.0 Comparative Example 7 69.0 151.6 295.1 1.85 0.24 1.05 1.0

Referring to Table 2, it can be seen that Examples 1 to 4 in which the citrate plasticizers having an alkyl group having 7 carbon atoms are applied are superior to those of Comparative Examples 1 to 7 and have excellent resistance to stress and significantly reduce the amount of migration loss. . In addition, it can be seen that the hardness, tensile strength, and elongation characteristics are superior to those of the comparative examples, and the liquid heating loss is also excellent.

Specifically, it can be seen that the tensile strength and elongation characteristics of Comparative Examples 1 to 3 in which the citrate to which the alkyl group having 4 to 6 carbon atoms is bonded are applied are considerably inferior to the Examples, and that the transition loss is also large, and the heating loss In addition, it can be confirmed that it appears poorly, and in Comparative Examples 4 and 5 in which the citrate with an alkyl group having 8 or 9 carbon atoms was applied, the tensile strength or elongation was slightly higher, but the transition loss was large and the plasticization efficiency was high. It can be seen that there is little resistance to stress as well. Furthermore, it can be seen that Comparative Examples 6 and 7 also generally have no superior physical properties compared to the Examples.

On the other hand, when comparing Examples 3 and 4 with Comparative Examples 6 and 7, all of these sets are obtained by applying a composition in which mixed citrate is mixed with non-mixed citrate as a plasticizer. As described above, in the case of Examples 3 and 4, since the carbon number is a citrate in which different substituents are bonded within the same range, it is expected that the range of changes in physical properties will be small. In the case of Comparative Examples 6 and 7, the difference was about 5% in the case of elongation, and the liquid heating loss was also about 3 times. It is confirmed that there is a difference in the product, and it can be seen that it is somewhat difficult to implement the product at an equivalent level.

Through this, when citrate with an alkyl group having 7 carbon atoms is applied as a plasticizer, the reproducibility of the physical properties is excellent, the overall properties, especially the transfer loss and resistance to stress can be greatly improved, and other properties are also reduced. It can be seen that an excellent plasticizer can be provided in a balanced aspect of all physical properties without becoming a problem.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention defined in the following claims are also present. It belongs to the scope of rights of

Claims (7)

A citrate plasticizer comprising at least compound 1 represented by the following formula (1):
[Formula 1]

In Formula 1, R ₁ to R ₃ are each independently an alkyl group having 7 carbon atoms.
The method of claim 1,
R ₁ to R ₃ in Formula 1 are each independently, a citrate plasticizer that is any one of an n-heptyl group and a 2-methylhexyl group.
The method of claim 1,
The citrate plasticizer is a citrate plasticizer comprising at least one selected from the group consisting of compounds represented by the following formulas 1-1 to 1-6:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

The method of claim 1,
The compound represented by Formula 1 is a citrate plasticizer comprising at least one non-mixed citrate represented by Formula 1-1 and Formula 1-2:
[Formula 1-1]

[Formula 1-2]

The method of claim 1,
The citrate plasticizer
An immiscible citrate represented by the following formulas 1-1 and 1-2;
A first hybrid citrate represented by the following Chemical Formulas 1-3 and 1-4; And
A citrate-based plasticizer comprising; a second hybrid citrate represented by the following formulas 1-5 and 1-6:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

100 parts by weight of resin; And 5 to 150 parts by weight of the citrate plasticizer of claim 1.
The method of claim 6,
The resin composition is at least one selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer.